The present invention relates to dyeing compositions comprising, in a medium appropriate for dyeing, at least one oxidation dye precursor and/or one or more couplers, a ketose as reducing agent and at least one laccase as oxidizing agent, to the use of the compositions for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair, to dyeing processes using the compositions, and to dyeing devices using the compositions.
It is known to dye keratinous fibers, and in particular the hair, with dyeing compositions comprising oxidation dye precursors generally known as xe2x80x9coxidation bases,xe2x80x9d in particular ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic bases.
Oxidation dye precursors are compounds, initially colorless or only slightly colored, which develop their dyeing power within the individual hair in the presence of an oxidizing agent. The oxidizing agent used is generally hydrogen peroxide. The formation of the colored compounds results either from a condensation of the xe2x80x9coxidation basesxe2x80x9d with themselves or from a condensation of the xe2x80x9coxidation basesxe2x80x9d with coloring-modifying compounds or xe2x80x9ccouplers,xe2x80x9d which are generally present in the dyeing compositions used in oxidation dyeing and which are represented more particularly by meta-phenylenediamines, meta-aminophenols, meta-diphenols and some heterocyclic compounds.
The variety of the molecules involved, which are composed, on the one hand, of the xe2x80x9coxidation basesxe2x80x9d and, on the other hand, of the xe2x80x9ccouplers,xe2x80x9d makes it possible to obtain a rich palette of colors.
The oxidation coloring of keratinous fibers can also be carried out using different oxidizing systems than hydrogen peroxide systems, such as enzymatic systems. For example, it is known in U.S. Pat. No. 3,251,742 and Patent Applications FR-A-2 112 549, FR-A-2,694,018, EP-A-0,504,005, WO 95/07988, WO 95/33836, WO 95/33837, WO 96/00290, WO 97/19998 and WO 97/19999, the disclosures of which are incorporated by reference herein, to dye keratinous fibers with compositions comprising at least one oxidation dye in combination with enzymes of the laccase type, these compositions being brought into contact with atmospheric oxygen. These enzyme systems are advantageous because it has been observed that aqueous hydrogen peroxide solution can result in damage to the hair fiber and, in addition, in partial attack on the melanin of the hair, which results in the fiber becoming lighter in color.
It has also been found that, in some cases, laccases make it possible to obtain satisfactory oxidation colorings by using only couplers, without oxidation bases. Thus, in the present invention, the term xe2x80x9coxidation dyexe2x80x9d covers oxidation dye precursors and/or couplers.
In order to be able to preserve oxidation dyes, i.e., oxidation dye precursors and/or couplers, it is necessary to combine them with a reducing agent. However, the inventor has found that these reducing agents generally slow down the absorption of the dyes on the fibers, which is reflected by less luminous shades and less intense colorings. In order to obtain an equivalent chromaticity, it is then necessary to use larger amounts of dyes.
Furthermore, numerous reducing agents used until now have an inhibiting effect on the activity of laccase.
After much research carried out in this field, the inventor has just discovered that the use of a ketose as reducing agent when a laccase is used as oxidizing agent makes it possible to solve the above-mentioned problems. This is because it has been found that ketoses do not inhibit the activity of laccase. It has also been found, surprisingly, that the mixture thus produced does not slow down the absorption of the oxidation dyes on the hairs.
Furthermore, these compositions give rise to more chromatic (more luminous) shades and to more intense colorings in comparison with equivalent compositions comprising conventional reducing agents and oxidizing agents. The colorings obtained also exhibit good resistance to perspiration, to light and to shampoos.
The invention also makes it possible to decrease the amount of coloring active materials used in dyeing compositions, in comparison with conventional techniques known in the prior art.
A subject of the present invention is thus the use of a ketose as reducing agent, in an amount ranging from 0.1 to 15% by weight with respect to the total weight of the composition, and of a laccase as oxidizing agent in oxidative dyeing.
Another subject of the invention relates to a process for dyeing keratinous fibers and in particular human keratinous fibers, such as the hair, which comprises:
applying, to the fibers, a dyeing composition (A) comprising, in a medium appropriate for dyeing, at least one oxidation dye and a ketose as reducing agent, in an amount ranging from 0.1 to 15% by weight with respect to the total weight of the composition (A), and
developing the color, in the presence of air, in an alkaline, neutral or acidic medium, using a laccase as oxidizing agent, the laccase either being incorporated in the composition (A), in which case the composition (A) is stored with air excluded, or in a composition (B), in which case the compositions (A) and (B) are mixed immediately before use or applied one after the other to the keratinous fibers.
The oxidation dye is preferably an oxidation dye precursor with optionally one or more couplers.
The oxidation dye can also be composed of one or more couplers, i.e., without oxidation dye precursors.
In a preferred form of the invention, the ketose is present in proportions ranging from 5 to 10% with respect to the total weight of the composition (A).
The ketoses according to the present invention are in particular C3-C8 ketoses, and preferably C6 ketoses (ketohexoses).
In particular, mention may be made, as examples of ketoses, of xylulose, ribulose, fructose, sedoheptulose, tagatose, sorbose and psicose. Their optical isomers (or enantiomers) in the D or L form can be used in the present invention, whether in the pure form (D or L) or in the paired form (D and L).
Fructose (D and/or L form) is particularly preferred.
The laccase or laccases used in the process according to the invention can be chosen in particular from laccases of plant origin, animal origin, fungal origin (yeasts, moulds or mushrooms) and bacterial origin, it being possible for the source organisms to be mono- or multicellular. The laccase or laccases can also be obtained by biotechnology.
Mention may be made, among the laccases of plant origin which can be used according to the invention, of the laccases produced by plants carrying out chlorophyll synthesis, as indicated in Application FR-A-2,694,018, the disclosure of which is incorporated by reference herein, such as those which are found in extracts of the Anacardiaceae, such as, for example, extracts of Magnifera indica, Schinus molle and Pleiogynium timoriense, and in extracts of the Podocarpaceae, Rosmarinus off., Solanum tuberosum, Iris sp., Coffea sp., Daucus carrota, Vinca minor, Persea americana, Catharenthus roseus, Musa sp., Malus pumila, Gingko biloba, Monotropa hypopithys (Indian pipe), Aesculus sp., Acer pseudoplatanus, Prunus persica and Pistacia palaestina. 
Mention may be made, among the laccases of fungal origin optionally obtained by biotechnology which can be used according to the invention, of the laccase or laccases resulting from Polyporus versicolor, Rhizoctonia praticola and Rhus vernicifera, as indicated in Applications FR-A-2,112,549 and EP-A-504,005, the disclosures of which are incorporated by reference herein, and those laccases disclosed in Patent Applications WO 95/07988, WO 95/33836, WO 95/33837, WO 96/00290, WO 97/19998 and WO 97/19999, the contents of which form an integral part of the present description and the disclosures of which are incorporated by reference herein, such as, for example, those resulting from Scytalidium, Polyporus pinsitus, Myceliophtora thermophila, Rhizoctonia solani, Pyricularia orizae, and their variants. Mention may also be made of those laccases resulting from Tramates versicolor, Fomes fomentarius, Chaetomium thermophile, Neurospora crassa, Coriolus versicol, Botrytis cinerea, Rigidoporus lignosus, Phellinus noxius, Pleurotus ostreatus, Aspergillus nidulans, Podospora anserina, Agaricus bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius piperatus, Russula delica, Heterobasidion annosum, Thelephora terrestris, Cladosporium cladosporioides, Cerrena unicolor, Coriolus hirsutus, Ceriporiopsis subvermispora, Coprinus cinereus, Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens, and their variants.
Laccases of fungal origin optionally obtained by biotechnology are particularly preferred.
The enzymatic activity of the laccases of the invention having syringaldazine among their substrates can be defined from the oxidation of syringaldazine under aerobic conditions. The lacu unit corresponds to the amount of enzyme catalysing the conversion of 1 mmol of syringaldazine per minute at pH 5.5 and at 30xc2x0 C. The u unit corresponds to the amount of enzyme producing a delta of absorbance at 530 nm of 0.001 per minute using syringaldazine as substrate, at 30xc2x0 C. and at pH 6.5.
The enzymatic activity of the laccases of the invention can also be defined from the oxidation of para-phenylenediamine. The ulac unit corresponds to the amount of enzyme producing a delta of absorbance at 496.5 nm of 0.001 per minute using para-phenylenediamine as substrate (64 mM), at 30xc2x0 C. and at pH 5.
The amounts of laccase used in the compositions of the invention will vary according to the nature of the laccase chosen. They will preferably vary from 0.5 to 3000 lacu or from 1000 to 6xc3x97107 u units or from 20 to 3xc3x97106 ulac units per 100 g of composition applied to the hair.
The oxidation dyes which can be used in the context of the present invention are chosen from those conventionally known in oxidation dyeing.
Mention may particularly be made of the following oxidation dye precursors:
the para-phenylenediamines of following formula (I) and the acid addition salts of these compounds: 
xe2x80x83in which
R1 represents a hydrogen atom or a C1-4 alkyl, C1-4 monohydroxyalkyl, C2-4 polyhydroxyalkyl or 4xe2x80x2-aminophenyl radical,
R2 represents a hydrogen atom or a C1-4 alkyl, C1-4 monohydroxyalkyl or C2-4 polyhydroxyalkyl radical,
R3 represents a hydrogen atom, a halogen atom, such as a chlorine atom, or a C1-4 alkyl, sulfo, carboxyl, C1-4 monohydroxyalkyl or C1-4 hydroxyalkoxy radical, and
R4 represents a hydrogen atom or a C1-4 alkyl radical.
Mention may particularly be made, among the para-phenylenediamines of formula (I) above, of para-phenylenediamine, para-toluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-amino-N,N-bis(xcex2-hydroxyethyl)-3-methylaniline, 4-amino-3-chloro-N,N-bis(xcex2-hydroxyethyl)aniline, 2-(xcex2-hydroxyethyl)-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(xcex2-hydroxyethyl)-para-phenylenediamine, N-(xcex2,xcex3-dihydroxypropyl)-para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-(xcex2-hydroxyethyloxy)-para-phenylenediamine and the acid addition salts of these compounds.
Among the para-phenylenediamines of formula (I), para-phenylenediamine, para-toluylenediamine, 2-isopropyl-para-phenylenediamine, 2-(xcex2-hydroxyethyl)-para-phenylenediamine, 2-(xcex2-hydroxyethyloxy)-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and the acid addition salts of these compounds are particularly preferred.
Mention may also be made of the following oxidation dye precursors:
the bisphenylalkylenediamines of formula (II) and the acid addition salts of these compounds: 
xe2x80x83in which
Q1 and Q2, which are identical or different, represent a hydroxyl radical or an NHR8 radical in which R8 represents a hydrogen atom or a C1-4 alkyl radical,
R5 represents a hydrogen atom or a C1-4 alkyl, C1-4 monohydroxyalkyl, C2-4 polyhydroxyalkyl or C1-4 aminoalkyl radical, it being possible for the amino group to be substituted,
R6 and R7, which are identical or different, represent a hydrogen or halogen atom or a C1-4 alkyl radical, and
W represents a radical chosen from the group formed by the following radicals:
xe2x80x94(CH2)nxe2x80x94, xe2x80x94(CH2)mxe2x80x94, xe2x80x94Oxe2x80x94(CH2)mxe2x80x94, xe2x80x94(CH2)mxe2x80x94CHOHxe2x80x94(CH2)mxe2x80x94 and
xe2x80x94(CH2)mxe2x80x94N(CH3)xe2x80x94(CH2)mxe2x80x94;
in which n is an integer ranging from 0 to 8, and m is an integer ranging from 0 to 4.
Mention may particularly be made, among the bisphenylalkylenediamines of formula (II) above, of N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)-1,3-diamino-2-propanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-diethyl-N,Nxe2x80x2-bis(4-amino-3-methyl-phenyl)ethylenediamine and the acid addition salts of these compounds.
Among these bisphenylalkylenediamines of formula (II), N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diamino-2-propanol or one of its addition salts with an acid is particularly recommended.
Mention may also be made of the following oxidation dye precursors:
the para-aminophenols corresponding to the formula (III) and the acid addition salts of these compounds: 
xe2x80x83in which
R9 represents a hydrogen atom or a C1-4 alkyl, C1-4 monohydroxyalkyl, (C1-4 alkoxy)(C1-4 alkyl), C1-4 aminoalkyl or hydroxy(C1-4 alkyl)amino(C1-4 alkyl) radical, and
R10 represents a hydrogen or fluorine atom or a C1-4 alkyl, C1-4 monohydroxyalkyl, C2-4 polyhydroxyalkyl, C1-4 aminoalkyl, cyano(C1-4 alkyl) or (C1-4 alkoxy)(C1-4 alkyl) radical, with the proviso that at least one of the R9 or R10 radicals represents a hydrogen atom.
Mention may particularly be made, among the para-aminophenols of formula (III) above, of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-(hydroxymethyl)phenol, 4-amino-2-methylphenol, 4-amino-2-(hydroxymethyl)phenol, 4-amino-2-(methoxymethyl)phenol, 4-amino-2-(aminomethyl)phenol, 4-amino-2-((xcex2-hydroxyethyl)aminomethyl)phenol, and the acid addition salts of these compounds.
The ortho-aminophenols which can be used as oxidation bases in the context of the present invention are chosen in particular from 2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene, 2-amino-1-hydroxy-6-methylbenzene, 5-acetamido-2-aminophenol and the acid addition salts of these compounds.
The heterocyclic bases which can be used as oxidation bases in the context of the present invention are chosen in particular from pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and the acid addition salts of these compounds.
Mention may more particularly be made, among the pyridine derivatives, of the compounds disclosed, for example, in Patents GB-1,026,978 and GB-1,153,196, the disclosures of which are incorporated by reference herein, such as 2,5-diaminopyridine, and the acid addition salts of such compounds.
Mention may particularly be made, among the pyrimidine derivatives, of the compounds disclosed, for example, in German Patent DE-2,359,399 or Japanese Patents JP-88-169,571, the disclosures of which are incorporated by reference herein, such as 2,4,5,6-tetraaminopyrimidine or 4-hydroxy-2,5,6-triaminopyrimidine, and the acid addition salts of such compounds.
Mention may more particularly be made, among the pyrazole derivatives, of the compounds disclosed in Patents DE-3,843,892 and DE-4,133,957 and Patent Applications WO-94/08969 and WO 94/08970, the disclosures of which are incorporated by reference herein, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole or 4,5-diamino-1-(4xe2x80x2-chlorobenzyl)pyrazole, and the acid addition salts of these compounds.
According to the invention, the oxidation dye precursor or precursors preferably represent from 0.0005 to 12% by weight of the total weight of the composition (A), and more preferably from 0.005 to 6% by weight approximately.
The couplers which can be used in the dyeing process according to the invention are those conventionally used in oxidation dyeing compositions, such as, for example, meta-phenylenediamines, meta-aminophenols and meta-diphenols (resorcinols), mono- or polyhydroxylated naphthalene derivatives, sesamol and its derivatives, and heterocyclic compounds, such as, for example, indole couplers, indoline couplers or pyridine couplers, and the acid addition salts of such compounds.
These couplers can be chosen in particular from 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)-amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 1-(xcex2-hydroxyethoxy)-2,4-diaminobenzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, xcex1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one and the acid addition salts of such compounds.
When they are present, these couplers preferably represent from approximately 0.0001 to 10% by weight of the total weight of the composition (A), and in particular from approximately 0.005 to 5% by weight.
The acid addition salts of the chromogenic compounds, namely the oxidation bases and the couplers, are chosen in particular from hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates.
In addition to the oxidation dyes defined above, the composition (A) can comprise direct dyes for enriching the shades with highlights. These direct dyes can be chosen in particular from nitro, azo or anthraquinone dyes.
The composition (A) and/or the composition (B) can additionally comprise at least one amphoteric or cationic substantive polymer, such as those defined in EP-A-0,673,641, the disclosure of which is incorporated by reference herein, among which it is preferable to employ:
the poly(quaternary ammonium) polymers prepared and disclosed in French Patent 2,270,846, the disclosure of which is incorporated by reference herein, which are composed of repeating units corresponding to the following formula (IV): 
xe2x80x83the weight-average molar mass of which, determined by gel permeation chromatography, ranges from 9500 to 9900; and
the poly(quaternary ammonium) polymers prepared and disclosed in French Patent 2,270,846, the disclosure of which is incorporated by reference herein, which are composed of repeat units corresponding to the following formula (V): 
xe2x80x83the weight-average molar mass of which, determined by gel permeation chromatography, is approximately 1200.
The medium of the composition (A) which is appropriate for dyeing is preferably an aqueous medium composed predominantly of water and optionally comprising cosmetically acceptable organic solvents, such as alcohols, for example ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, and glycols or glycol ethers, such as ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers, such as propylene glycol monomethyl ether, butylene glycol, and dipropylene glycol and the alkyl ethers of diethylene glycol, such as, for example, diethylene glycol monomethyl or monobutyl ether. When organic solvents are present, they are preferably used in concentrations ranging from approximately 0.5 to 20% by weight, preferably from approximately 2 to 10% by weight, with respect to the total weight of the composition.
The composition (A) can also comprise an effective amount of other agents commonly used in the field of oxidation dyeing. These adjuvants can include, for example, sequestering agents, hair conditioning agents, in particular silicones, preserving agents, opacifying agents, and the like, and anionic, nonionic or amphoteric surface-active agents or their mixtures.
Of course, a person skilled in the art will take care to choose the optional additional compound or compounds mentioned above so that the advantageous properties intrinsically attached to the dyeing composition according to the invention are not, or virtually not, detrimentally affected by the envisaged addition or additions.
The values of the pH of the compositions (A) and (B) can be chosen in particular so that the value of the pH of the ready-for-use composition, resulting from the mixing of the dyeing composition (A) and of the oxidizing composition (B), generally ranges from 3 to 11, preferably from 4 to 9, and more preferably from 6 to 8. They can be adjusted by means of acidifying or basifying agents well known in the art of the oxidation dyeing of keratinous fibers.
Mention may be made, among basifying agents, of, for example, ammonia, alkaline carbonates, alkanolamines, such as mono-, di- and triethanolamines and their derivatives, sodium hydroxide, potassium hydroxide and the compounds of the following formula (VI): 
in which R is a propylene residue optionally substituted by a hydroxyl group or a C1-4 alkyl radical, and R11, R12, R13 and R14, which are identical or different, represent a hydrogen atom or a C1-4 alkyl or C1-4 hydroxyalkyl radical.
The acidifying agents are conventionally, by way of example, inorganic or organic acids, such as hydrochloric acid, orthophosphoric acid, carboxylic acids, such as tartaric acid, citric acid or lactic acid, or sulphonic acids.
Another subject of the present invention is a ready-for-use composition for the dyeing of keratinous fibers comprising the laccase and the oxidation dye and at least one ketose, or which is capable of being obtained by mixing the compositions (A) and (B) defined above.
Another subject of the invention is a process for dyeing keratinous fibers and in particular human keratinous fibers, such as the hair, employing the dyeing compositions as defined above.
According to this process, at least one ready-for-use dyeing composition as defined above is applied to the fibers for a time sufficient to develop the desired coloring, after which the hair is rinsed, optionally washed with shampoo, rinsed again and dried.
The time necessary for the development of the coloring on the keratinous fibers generally ranges from 3 to 60 minutes, and more specifically from 5 to 40 minutes.
The application of the ready-for-use dyeing composition can take place in particular at a temperature ranging from room temperature (20xc2x0 C.) to 60xc2x0 C., and preferably from 35 to 50xc2x0 C.
According to a specific embodiment of the invention, the process comprises a preliminary stage which comprises separately storing, on the one hand, a composition (A) as defined above and, on the other hand, a composition (B) defined above, and then mixing them at the time of use before applying this mixture to the keratinous fibers.
Another subject of the invention is dyeing multi-compartment devices or dyeing kits comprising at least two compartments, one of which contains a composition (A) comprising at least one oxidation dye and a ketose in an amount ranging from 0.1 to 15% by weight of the total weight of the composition (A), and another of which contains an oxidizing composition (B) comprising at least one laccase. These devices can be equipped with a means, such as the devices disclosed in Patent FR-2,586,913, the disclosure of which is incorporated by reference herein, which allows the desired mixture to be delivered to the hair.
It is clearly understood that the description which precedes has only been given purely by way of illustration and without implied limitation and that alternative forms or modifications can be introduced thereto within the scope of the present invention.